Antifouling paint compositions and process of making the same



Patented June 8, 1948 ANTIFOULING PAINT COIWPOSITIONS AND PROCESS OF MAKING THE SAME Charles J. Greenstreet, Summit, N. J., assignor to Universe Holding Corporation, New York, N. Y., a corporation of New York No Drawing. Application July 27, 1943, Serial No. 496,305

7 Claims. (Cl. 106-15) This invention relates to new organic powerful ptomaine poisons, particularly for ship bottoms paint and coatings to prevent barnacle and like deposits on ships, aeroplane pontoons, wharves,

ment like slime substance containing calcium carbonate and this material adheres to the surface of metal, wood or other material on which barnacles intend to fasten themselves. The barnacle thus uses this material which leaves a deposit of calcium carbonate to fasten itself to whatever surface is in its immediate neighborhood. Therefore, any poison as set out below which will kill the barnacle before it can even attach itself to a surface will prevent barnacle deposits.

Bacteria are unicellular forms of vegetable life and the excretions of bacteria that feed on nitrogenous products are. ptomaines or toxins. These unicellular bacteria that feed on the nitrogenous barnacles excrete the toxins and ptomaines that I use to cause paralysis and almost instant death to barnacles, bryozoans, marine algae and the like. It is well known that there are large series of ptomaines and poisons formed by bacteria feeding on nitrogeneous material and in the decomposition and putrefaction of the nitrogenous barnacles there is formed amines and diamines and amino acids, etc., although the original amino esters may be basic in character. I have discovered certain of these ptomaines which are extremely poisonous such as mytilotoxin, CGHIENOZ, and its homologues which commonly occur in decomposed mussels and often in small proportions even in living mussels, may be artificially cultivated under suitable conditions and according to the process hereinafter set forth, the material incorporating m ilotoxin and its toxic homologues or like poisons s mixed with a proper proportion of carriers to form a protective paint or plastic coating and the like. Among the putrefactive bacteria responsible for the development of the poisonous ptomaines which I employ are Clostridium aerofoetidum, C. bifermentans, C. histolyticum, C'. Zeutoputrescens, C. ovalarz's, C. parabotulinum, C. parasporogenes, C'. putrefaciens, C. sporogenes, and C. tyrosz'nogenes.

As one example of my invention, I take barnacles at the seed stage before any shell is formed thereon, andthese barnacles are partially dehydrated and then in a mass not over a foot in depth are gradually allowed to decompose. This decomposition preferably takes place at a temperature between 50 and degrees Fahrenheit, and during the progress of the same, the mass is'turned over occasionally so as to provide the necessary contact with the oxygen of the air and normally the maximum putrefaction will take place in about six to seven or so days.

Samples of the mass are taken from time to time to test the progress of the decomposition. When the percentage of mytilotoxin or other like toxic ptomainesas determined by chemical analysis or by experience is found at its maximum, further decomposition is stopped by drying the mass at a temperature of from to degrees Fahrenheit but under conditions so that the mytilotoxin or other poisons are not destroyed, and it is then finely ground. The material then is mixed with the mass vehicle or carrier such as low water absorption plastics such as methyl methacrylate, vinyl copolymers or phenol formaldehyde, linseed oil paints, tung oil paints, varnishes or the like, not less than three per cent of the ground dried material being mixed with the vehicle to form an effective protective composition for ships bottoms, aeroplane pontoons and the like.

Instead of mixing the dried material containing mytilotoxin and other toxic ptomaines, it may also be treated with metallic copper, copper oxide, or copper carbonate to form copper salts of mytilotoxin which can beused in paints, varnishes or other coatings or'as insecticide sprays or one can use other metallic oxides or carbonates to form the corresponding saltof mytilotoxin or other toxins.

I have also found that the dried material as above prepared may also be mixed with synthetic plastics in liquid or powdered form incorporated in the plastic carrier and will impart their protective qualities to such plastics.

A particularly powerful concentrated extract of mytilotoxins and its homologues and other soluble toxins can be made by extracting the fully decomposed barnacle material or other nitrogenous material with water or other solvent, evaporate the excess water or solvent at a temperature that does not destroy any of the toxic ptomaines, then separate the soluble toxins from the inert materialby filtration and use either as set out above for dry material or mixed with metallic oxides or carbonatesto form water insoluble salts.

While I have shown here in this embodiment the manufacture of this protective; material by compositioncomprising a water-resistant coating vehicle in which is incorporated a dry powder resultingfrom the decomposition and putrefaction ot-barnacles and containingtoxic ptothe decomposition of barnacles,*it will'be obvious 5; maines and poisons resulting from said decomthat similanprotec'tive ,material may be made by position,'-;and putrefaction, inan amount sufiL decomposing mussels, oysters, shell fish, plankcient for substantially preventing adhesion of ton, fish, meat, and other materials which form barnacles and the like on said ships bottoms and toxic ptomaines under certain conditions of de-w similar surfaces.

composition and which ptomainesor toxins when w process of preparing a paint composition properly incorporated into protelc a j ion protecting shipsbottoms and similar surfaces tions may beused;as above indicate exposed to 'sea Water, said process comprising vious that the toxins, when once incorporated, collecting; barnacles-in the seed stage, subjecting into a protective vehicle such asa plasticopati g; l same tmdeeomposition and putrefaction by perof those plastics of low water absorption capacity; 153. mitting, saidbarnacles to stand in contact with or an oil paint or the like, will notsufijerfurti er, ..air untila maximum of toxicity of the decomdeoomposition and such paints will retaingthe'irj; .pnsedprodu'ct is attained, inhibiting further depotency fora period of time covering practically composition in the seed mass by drying said mass all commercial purposes. and'iinicorporating same into a water-resistant The temperatures above given for the decom paint vehicle in an amount sufficient for subposition of jthe source material Y andior: drying stantially preventing: adhesion of ;-b,arnac-1es.;.and samea-re approximate merelyand,-I do not, wish the, like, on said, ships bottoms and s ta hei itedto-these xact t mp ratures, sur aces. i e

av n .iu ytd s ribedlmv n ent m wb tzl 1-Amt 2 fd ine a m osii pn. 9 7 claim is; Q protecting. ships bottoms andsimiiar su 1 Aprotectie compositiomfor ships bottoms exposed to sea water, said process-com r g and s milar surfaces exposed to sea water, said gathering :seed barnacles, subjecting same to; decomp siti n .cnm ris g ,Wa er l1t-coat mp s tiq and l qu f c on at a-t mnera ure s; vehicle, and.- r iqomain c rp rat d o r -8 F renhe oppin am-I es therein in anamount 'suiiigientgforsubstantially composition andputrefaction in the-seed mass preventing adhesionbf rbarnacles andthe like when the maximumof toxicity oftheadecom on said ships bottoms andsimi lar surfaces. posed product is attained by,dryinasaid-massand 2;.A- .P1.Qi ,6 QtiVe, composition for; ships bottoms incorporating said mass -inga water-resistant and; milar surfaces exposedrto sea water, said paint vehicle inran amount sufficient .forsubcomp ion; comprising a water-resistant coatstantiallypreventingadhesion i .barnacles and; ingyveh cle, and mytilotoxineincorporatedtherein the vlike. on, said ships: bottoms andsimilar inan a nountsufiicient\fonsubstantiallyprevent: surfaces. p I v ins adhes n fl iiHia G fiQd h li e onv s I CHARLES seams ess? shipsbottomsand-similar surfaces. V r V l t 3. :A'GQmPQ Vitionrior protecting ships bottoms i0 I BEE ENQES CITED,

. 3 u ac s d qx fi Water, e The following-references arexof.reoord:..inu.the omp ,1 ;ieon; iqmn in w wa e s b file of this tent; a, plasticinlwhichiis incorpor, ted; the toxic :pto: v 1 maines and poisons, resulting from the decompo- Nl D S 35 ion andputr fa tion- I-; 1 ge eri s Number Name-v Date: inanamount su fi ent fqr bs a ial v re n 2,287,218 -Younget a1 jJur -1e..2-3,"194 2 mg; adhesion ofbarnacles nd h l k said 1,960,251 Mano Man. .-29, 1 a3i ships: bottomsv and similarsuriaccsh b t 1 1,960,250; Mano ;l VIar. '29,;193fi 4; Acomp'ositionfor'protectings ,ips, 0t oms r and similar surfaces.exposedtosea-water, said g EQR'E N ATWTS composition comprising a water-resistant paint N b Country Date: vehicle; in-WhiQh lfp fi ii d h s c D -10,328- Great Britain ,of 1 909 maines and: p isons resu t n -f m hevdepom es?- GreatBritain unn ;o1?118631 positionrand,putrefaction ;of;nitrogen0us mate- OTHER- BEFERENCE'S rials, in; an amount sufficient ior substantially preventingadhesion of barna'cles and the likeon saidv ships bottoms andxsimilara surfaces.-

5;. A' composition: fornprotecting, ships bottoms and similar suriacesexposed to seawater, said huh, M.

. aChkfs Chemical-1 Dictionary, 2 nd 1 193; page 7.63. i A

.Tanner, Bacteriology; 3rd ed, 1933, pagea 3- 5 352. I 

